1. Field of the Invention
The present invention relates to a process for reducing the concentration of acidic contaminates in fluorinated hydrocarbons by contact with a phosphorous oxyacid salt.
2. Description of Related Art
Chlorine- and bromine-substituted fluorinated hydrocarbons have long found applications as refrigerants, blowing agents, propellants, solvents, and fire extinguishants. However, dissociation of these materials in the atmosphere has been linked to depletion of stratospheric ozone. Many of these materials have been replaced by fluorinated hydrocarbons that contain only carbon, hydrogen, and fluorine (i.e., hydrofluorocarbons or HFC's). Examples of such hydrofluorocarbons include 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3 or HFC-227ea, an aerosol propellant and fire extinguishant), 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3 or HFC-236fa, a fire extinguishant and refrigerant), 1,1,1,3,3-pentafluoropropane (CF3CH2CHF2 or HFC-245fa, a polymer foam blowing agent), and 1,1,1,2-tetrafluoroethane (CF3CH2F or HFC-134a, a refrigerant and aerosol propellant).
Commercial manufacturing processes for hydrofluorocarbons often involve addition of HF, an inorganic acid, to olefins. For example, HFC-227ea is prepared by addition of HF to hexafluoropropene (see U.S. Pat. No. 6,281,395). Other processes involve reacting HF with chlorinated hydrocarbons such as chloroolefins, chloroalkanes, or partially fluorinated chlorocarbons. For example, HFC-236fa is prepared by reacting HF with 1,1,1,3,3,3-hexachloropropane and HFC-245fa is prepared by reacting HF with 1,1,1,3,3-pentachloropropane (see U.S. Pat. No. 6,291,730). In this type of exchange process, HCl, an inorganic acid, is formed as a by-product of the substitution of fluorine for chlorine. Other hydrofluorocarbon manufacturing processes involve replacement of a chlorine substituent in a chlorofluorocarbon or a hydrochlorofluorocarbon with a hydrogen substituent by reaction with hydrogen with elimination of HCl. For example, HFC-134a is prepared by reaction of hydrogen with 1,1-dichloro-1,2,2,2-tetrafluoroethane (see U.S. Pat. No. 5,208,397) and HFC-236fa is prepared by reaction of hydrogen with 2,2-dichloro-1,1,1,3,3,3-hexafluoropropane (see International Patent Application No. 96/17,813).
Fluoroolefins such as hexafluoropropene (C3F6, HFP) and 1,1,3,3,3-pentafluoro-1-propene (CF3CH═CF2, HFC-1225zc) are another class of fluorinated hydrocarbons of commercial interest; these compounds are often useful as polymer intermediates. Fluoroolefins may be prepared under conditions where acidic contaminants may be present. For example, U.S. Pat. No. 5,057,634 discloses a process for preparation of hexafluoropropene comprising as a final step hydrodehalogenating CF3CClFCF3 in the presence of hydrogen and a catalyst. U.S. Pat. No. 6,093,859 discloses a process for producing HFC-1225zc involving dehydrofluorinating HFC-236fa at an elevated temperature in the vapor phase over a catalyst.
The crude product in the aforementioned processes may be contaminated with hydrogen chloride (HCl) and/or hydrogen fluoride (HF). Removal of HCl and HF is usually accomplished by distillation, but traces of these acidic contaminants often remain in the product. Even after distillation, fluorinated hydrocarbons may remain contaminated with HF or HCl due to the formation of azeotropes or azeotrope-like compositions; that is constant-boiling mixtures that behave as a single substance. For example, it has been disclosed that HFC-227ea forms an azeotrope with HF (see U.S. Pat. No. 6,376,272) and HFC-236fa forms an azeotrope with HF (see U.S. Pat. No. 5,563,304). These acidic contaminants must be removed from the hydrofluorocarbons prior to commercial use.
It is well-known that acidic contaminants in perhalogenated fluorocarbons (e.g., CCl2F2) may be removed by treatment with a strong base such as sodium hydroxide without degradation of the perhalogenated fluorocarbon. However, substitution of one or more hydrogen substituents in a saturated hydrocarbon by a halogen (i.e., fluorine, chlorine, bromine, or iodine) often increases the acidity of at least some of the remaining hydrogen substituents (see the discussion by Reutov, Beletskaya, and Butin on pages 51 to 58 in CH-Acids, Pergamon Press, Oxford, (1978)). Depending on the particular arrangement of hydrogen and halogen substituents, exposure of a saturated partially halogenated hydrocarbon to a base such as sodium hydroxide may result in facile elimination of the corresponding hydrogen halide from the halogenated hydrocarbon by dehydrohalogenation, which is the elimination of hydrogen halide from a saturated halogenated hydrocarbon to produce an unsaturated halogenated compound. The unsaturated compound so formed can be acyclic (linear or branched) or cyclic, depending upon the starting halogenated hydrocarbon.
Therefore, removal of acidic contaminants from saturated halogenated hydrocarbons by contacting mixtures of saturated halogenated hydrocarbons and HF or HCl with strong bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, may result in the formation of substantial amounts of unsaturated compounds (e.g., amounts greater than 5 weight per cent of the starting halogenated hydrocarbon) due to elimination of hydrogen halide through dehydrohalogenation. For example, as disclosed in the examples herein, contact of HFC-227ea with strong base gives some hexafluoropropene, contact of HFC-236fa with strong base gives some 1,1,3,3,3-pentafluoro-1-propene, contact of HFC-245fa with strong base gives some 1,3,3,3-tetrafluoro-1-propene, contact of 2,3-dichloro-1,1,1,3,3,3-pentafluoropropane (CF3CHClCClF2, HCFC-225da) with strong base gives some 2-chloro-1,1,3,3,3-pentafluoro-1-propene, and contact of 1,1,1,2,2,3,4,5,5,5-decafluoropentane (CF3CF2CHFCHFCF3, HFC-43-10mee) with strong base gives some nonafluoropentenes.
U.S. Pat. No. 6,187,976 example 5 discloses a liquid phase fluorination process for CCl3CH2CCl3. The product stream consisting of HCFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), 1,1,3,3,3-pentafluoropropene, HF, HCl, and other minor products is passed through a caustic scrubber. The acid-free product stream contains 25% 1,1,3,3,3-pentafluoropropene.
Because unsaturated fluorocarbons are frequently toxic, their presence in a hydrofluorocarbon product is undesirable. Removal of such unsaturated compounds by distillation is often difficult due to the fact that they may have boiling points close to those of the hydrofluorocarbons or they may even form azeotropes or azeotrope-like mixtures with the hydrofluorocarbons. Thus, formation of unsaturated impurities during a neutralization process is not only a yield loss, but results in the need for additional purification steps which add to the overall cost of the manufacturing process.
Highly fluorinated olefins such as HFP and HFC-1225zc are well-known to be reactive toward nucleophiles (e.g., the anionic portion of a compound such as sodium hydroxide where the hydroxide ion is the nucleophile). Therefore, removal of acidic contaminants from highly fluorinated olefins by contacting mixtures of highly fluorinated olefins and HF or HCl with strong bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, may result in nucleophilic attack by hydroxide ion at the double bond with hydrolysis (i.e., replacement of the fluoride ion by hydroxide ion) of the olefin and formation of fluoride ions. This can result in a substantial yield loss, such as a yield loss of greater than 5 weight percent of the starting fluorinated olefin. World Intellectual Property Organization patent application publication no. WO 96/29,296 discloses a method for producing fluoroalkanes by high-temperature pyrolysis of chlorodifluoromethane in the presence of an alkane or fluoroalkane. The products of said process are scrubbed with caustic soda prior to isolation (page 3, lines 3, 4, and 5); little fluoroolefins are observed in the products and apparently about 40% of the yield is not to useful products.
There is an industry need for a process to remove acidic contamination from saturated and unsaturated fluorinated hydrocarbons in which the dehydrohalogenation of saturated fluorinated hydrocarbons or hydrolysis of unsaturated fluorinated hydrocarbons is reduced. The present invention meets that need.